A chemical process that recovers the vanadium contained in inorganic acid solutions, precipitating it as a solid compound of vanadium and alkali metal or monovalent cation ferrocyanide, is disclosed. Separation is carried out electrochemically, depositing the compound onto a metal immersed in the acid solution that contains vanadium as well as other dissolved metals, to which a ferrocyanide salt of an alkali metal or a monovalent cation has been previously added. If the inorganic acid present in solution is different than nitric acid, the vanadium can also be separated by direct addition of a ferrocyanide salt of an alkali metal or a monovalent cation to the acid solution containing vanadium. The method described allows recovery of vanadium without modifying the initial composition of the solution, except for the concentration of the vanadium dissolved.